Catalyst support and related processes

ABSTRACT

The present invention describes a catalyst support, which is used as an inorganic carrier for a Ziegler-Nata catalyst (ZN), using a modified spray cooling method. Such a catalyst support is prepared from alcoholic solutions of (a) an inorganic compound, in which the inorganic compound is a magnesium compound and (b) an inorganic compound and one or more additives. The solutions are prepared at a temperature below 100° C., carried through a nozzle placed inside a reactor, and sprayed into droplets forming a solid precipitate, which is generally spherical, when in contact with an inert hydrocarbon solvent at low temperature. The obtained catalyst support is reacted with a titanium compound, preferably titanium tetrachloride, in order to produce an active catalyst for olefin polymerization.

BACKGROUND OF THE INVENTION

Catalytic supports based on magnesium compounds, particularly magnesiumchloride (MgCl₂), are the most effective for the production ofZiegler-Natta (ZN) catalysts for olefin polymerization. Perhaps one ofthe main advantages to use an inorganic carrier for a ZN catalyst is thecontrol of the morphology, which enables the production of polymer withpredictable shape, bulk density and particle size distribution due tothe replica phenomenon. Given the importance of the support nature andits crystallization, it is important to explore alternatives routes forsupport preparation.

Since the early 1970s, the patent literature and scientific articleshave described routes to prepare spherical support from magnesiumhalides. One of the most important and widely used routes to obtainspherical and porous particles is by oil emulsion. This method isdescribed, for example, in the U.S. Pat. Nos. 4,469,648, 4,399,054,5,578,541, and 6,861,385. Such documents describe a catalyst obtainedfrom a support based on the formation of an emulsion of a fused productbetween MgCl₂ and alcohol at high temperature (120° C.) and pressure(9.8 bar) followed by subsequent precipitation of this emulsion in anon-solvent medium at low temperature. Furthermore, U.S. Pat. No.6,323,152 teaches that a long contact period (longer than 10 hours) isrequired for a complete melting between the mixture components in oil(MgCl₂ and alcohol).

In another approach, spherical particles are obtained through aSpray-Drying technique, as mentioned in U.S. Pat. No. 6,982,237,EP0123767, U.S. Pat. Nos. 4,376,062, and 4,311,817. In this case, thesolution is fed to the equipment by pumping and passing it through anatomizer at high temperature. The solvent evaporates in a chamber toform spherical dried particles. The product is separated in the cyclonefrom the gas and it is collected in a vessel followed by a solventrecovering step from the upper part of the cyclone. However, in thisprocess it is necessary to control several parameters, for example;feeding rate, gas flow to spray, temperature of gas flow to spray, flowrate of carrier gas in a chamber, and temperature of carrier gas.Additionally, this process involves evaporation of the solvent forsubsequent precipitation of the solid, which contributes to the particleformation. Thus, this technique is highly dependent on experimentalconditions. For example, rapid removal of alcohol can lead to formationof fragile hollow particles, which are not suitable for the productionof ZN catalysts due to the poor mechanical strength of the particles.

On the other hand, U.S. Pat. No. 4,421,674 describes catalyst supportswhich are obtained through a similar Spray-Drying technique. Itdescribes the application of a solution of MgCl₂ with alcohol, which isheated from 40 to 100° C. This solution is then dispersed through aspray nozzle and the solvent evaporates at high temperature,approximately 180° C. In this case, a large amount of solvent is carriedinto the Spray -Dryer, reducing the holding capacity of the solvent(vapor) in the gas stream and which may result in high content of thesolvent in the final product. It is worth noting that limitedinformation was given concerning the support morphology in U.S. Pat. No.4,421,674, and the catalyst obtained was evaluated only for ethylenepolymerization carried out at low pressure.

Another route to spherical support production is through a Spray-Coolingtechnique, as mentioned in U.S. Pat. No. 4,829,034. A solution,suspension or melted product is atomized into a spray of fine dropletsof spherical shape inside a spray cooling chamber. In this case thedroplets meet the inert gas stream at low temperature, which solidifiesthe droplets. A mixture of magnesium compound, alcohol, and internalelectron donor in molten state is then pumped to a nozzle and sprayeddroplets meet the cold inert gas or fluid, which flows from bottom totop of the spray cooling chamber, to form spherical particles. EuropeanPatent EP0700936 describes a process for producing a solid catalystcomponent for olefin gas phase polymerization from a mixture of amagnesium compound with an alcohol which is sprayed in a molten stateinto a spray column. Simultaneously, the inside of the spray column iscooled down to a temperature at which a solid component (B) is obtainedwithout any substantial vaporization of the alcohol in the mixture (A),to obtain the solid (B), followed by partial removal of the alcohol fromthe solid (B) between 20° C. and 60° C. under reduced pressure, toobtain a solid component (C).

In both cases a molten mixture is used and sprayed into a spray columncontaining a gas or fluid at low temperature to obtain a solid componentcatalyst. In this process, like the Spray-Drying process, is necessaryto control many variables such as: feeding rate, gas flow to spray, flowrate of carrier gas in a chamber, temperature of the carrier gas, heatedpipe for transferring the solution above 100° C., homogeneity of gasthroughout the system, temperature control to maintain the gas supply,and the precipitation chamber. All these factors may lead to a morecomplex and expensive process.

In yet another approach, patent application WO2014095523A1 describes theuse of a spray cooling technique as an alternative process to solidify afused Mg(OR¹)₂ and alcohol adduct in a cold liquid, in the absence of aninert liquid dispersant. The melted mixture of Mg(OR¹)₂ and alcoholcould be sprayed through a device in a low temperature environment tocause the solidification of particles. Thus, it suggests that thesupport preparation process undergoes processing under high temperatureand pressure conditions.

SUMMARY OF THE INVENTION

Described herein are novel catalyst supports as well as a process ofmanufacture and use. Distinctions over traditional spray cooling andspray drying techniques and the differences among properties of thefinal catalyst support are described below.

The present invention includes a process for manufacturing a catalystsupport component comprising an inorganic compound, an alcohol ROH, andan additive to increase the solubility of the inorganic compound in thealcohol ROH, comprising the steps of: a) dissolving the inorganiccompound and additive in the alcohol ROH to form a solution in a reactorat or below 100° C. in an inert atmosphere at a pressure between 1 and 5bar; b) transferring the solution to an atomizer; c) atomizing thesolution to form droplets; d) contacting the droplets with a non-solventliquid at a temperature between 10° C. and −30° C. to precipitatespherical particles; e) separating the non-solvent liquid from thespherical particles; and f) washing and drying the spherical particlesto form a catalyst support.

-   (i) In the present invention, the temperature to prepare the    solution of MgCl₂, additive, and alcohol is below 100° C., and from    50° C. to 70° C. in some embodiments. Contrarily, known prior art    teaches values in excess of 100° C.-   (ii) The present invention does not require preparation of a molten    mixture, which permits the use of milder conditions. For example,    the initial mixture to obtain the alcoholic solution can be prepared    for about 1-3 hours in a vessel (such as Reactor A of FIG. 1 below)    and under low pressure (less than 2 bar). Moreover, there is a    reduction in energy consumption, as well as greater simplicity and    operational safety in the overall process.-   (iii) The alcoholic solution comprises an inorganic compound, an    alcohol ROH, and an additive. The alcohol ROH consists of a R chosen    from a C1-C18 hydrocarbon group, and the additive can be a fluorine    based additive.-   (iv) The precipitation of solid particles occurs through the passage    of said alcoholic solutions into an atomizer located inside a    reactor under inert atmosphere and pressure between 1 and 2 bar. The    reactor contains a non-solvent hydrocarbon at low temperature. The    solution is sprayed into small droplets, which is carried to the    atomizer by the controlled pressure of the inert gas applied on the    alcoholic solution. This procedure has fewer variables when compared    to conventional processes such as spray cooling. Further, the use of    low temperature and low pressure promote much longer crystallization    times to form spherical particles.

The prepared catalyst support is generally spherical and hasdemonstrable activity for olefin polymerization, as seen herein.

A catalyst support is prepared by a modified Spray Cooling method,comprising (a) an inorganic compound, such as a magnesium compound; (b)an alcohol ROH, wherein R can be chosen from a C1-C18 hydrocarbon group;and (c) one or more additives, such as hydrofluoroalkenes (HFAs),polyaryletherketone (PAEK) derivatives, poly(oxy-1,2-ethanediyl)derivatives, aliphatic polyether, polylactic acid and polysorbates. Morespecifically, the one or more additives may be:1,1,1,2-tetrafluorethane; 1,1,1,2,3,3,3-heptafluoropentane;1,1,1,2,2,3,4-heptafluoropentane; 1,1,1,2,2,3,4-heptafluorobutane;1,1,3,3,4,4-hexafluorobutane; 1,1,1,2,3,4-hexafluorobutane;1,1,1,2,2,3,3,4,4-nonafluorohexane; 1,1,1,2,2,3,3,4,5-nonafluorohexane;1,1,1,2,2,3,3,4-octafluoropentane; 1,1,1,2,2,3,5-heptafluoropentane;1,1,1,2,2,3,4,5-octafluoropentane; 1,1,1,2,2,4,4,5,5-nonafluoropentane;1,1,1,2,3,4,4,5,5,5-decafluoropentane; sorbitan trifoliate, sorbitanmonooleate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate,polyethylene sorbitan monooleate, natural lecithin, oleylpolyoxyethylene ether, stearyl polyoxyethylene ether, laurylpolyoxyethylene ether, block copolymers of oxyethylene and oxypropylene,oleic acid, synthetic lecithin, diethylene glycol dioleate,tetrahydrofurfuryl, oleate, ethyloleate, isopropyl myristate, glycerylmonooleate, glyceryl monostearate, glyceryl monoricinoleate, cetylalcohol, polyethylene glycol, polyoxypropylene glycol, cetyl pyridiniumchloride, olive oil, glyceryl monolaurate, polyoxyethylene nonylphenolether, polyoxyetheylene monolaurate, polyetylenoglycol-b-polypropylene, oleic acid polyoxyethylene dilaurate, polyoxyethylenestearyl ether, polyetheretherketone, polyetherketone,polyetherketoneketone, polyetherketoneetherketoneketone,polyetheretherketoneketone.

The amount of additive in the inorganic support obtained show at least0.01 to 20 wt %. The catalyst support prepared has a distinct X-raydiffraction pattern and melting endotherm profile when compared to theprior art described in this document. In an embodiment of the invention,the catalyst support has at least one peak as shown by X-Raydiffraction, wherein only one peak is in the range from 0° to 10°.

Complementary melting profiles of the MgCl₂.nEtOH adduct using DSCthermogram are an important parameter to distinguish the physicalproperties of the prepared inorganic support. Claims regarding thephysical properties of supports obtained by oil emulsion technique, suchas the one showed in the patent WO1998044009 (where, MgCl₂.mROH.nH₂Oadduct, where R is a C1-C10 alkyl, 2≦m≦4.2, 0≦n≦0.7), described that thethermal profile do not show peaks at temperatures below 90° C. For peakspresented below 90° C., the fusion enthalpy associated with said peaksis less than 30%. The maximum peak occurs at temperatures between 95 and115° C. In U.S. Pat. No. 7,060,763, the MgCl₂.mEtOH adduct (m=2.5 to3.2) was characterized by a DSC profile having a single meltingtemperature (Tm) peak over 109° C., with an associated fusion enthalpy(ΔH) of 103 J/g or lower. U.S. Pat. No. 7,087,688 claimsMgCl₂.mEtOH.nH₂O adduct (3.4<m≦4.4 and 0<n≦0.7) with only one meltingpeak between 90-105° C. and associated fusion enthalpy lower than 125J/g in the DSC profile.

The catalyst support of the present invention has a unique DSC profile.For example, the DSC profile can have at least a first thermaltransition peak between 112° C. and 154° C. It can also have a secondthermal transition peak between 181° C. and 215° C. Further still, itcan have a third thermal transition peak between 235° C. and 248° C. asshown by DSC.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will be described by way of example withreference to the accompanying drawings.

FIG. 1 is an illustration of the apparatus used to prepare catalyticsupport.

FIG. 2 is a DSC thermogram of the supports SSB01 to SSB08.

FIG. 3 displays powder X-ray diffraction patterns of MgCl₂ and supportsamples SSB01 to SSB08.

FIG. 4 displays thermogravimetric analysis (TGA) of support samplesSSB01 to SSB08.

FIG. 5 are images obtained by Scanning Electron Microscope (SEM).

DETAILED DESCRIPTION OF THE INVENTION

For purposes of the description hereinafter, it is to be understood thatthe embodiments described below may assume alternative variations andembodiments. It is also to be understood that the specific articles,compositions, and/or processes described herein are exemplary and shouldnot be considered as limiting.

The present invention describes a catalytic support prepared using amodified Spray Cooling method. The production system is exemplified inFIG. 1, which illustrates the process steps to transfer, spray, andprecipitate to obtain spherical inorganic particles used to support a ZNcatalyst. The solution is first prepared in the reactor A (1). Thesolution is transferred through ⅛ inch tubing (2) containing a jacket tocontrol temperature during the transfer of the solution (3). The sizeand shape of the droplets produced by the atomizer are controlled by theliquid pressure (4) and gas pressure—optional (5). The type of atomizer(6) is not limited and different types can be explored according to thescale and conditions of the experiment. The crystallization of theparticle occurs through the contact of the droplets of alcoholicsolution with the inert hydrocarbon liquid at low temperature in thereactor B (7). All steps were conducted under nitrogen or argonatmosphere. In the examples described in this invention the catalystsupports are produced using two nozzle systems: gas atomizing andhydraulic spray nozzle. In the case of using gas atomizing theatomization is produced by combination of inert gas and liquidpressures. In the case of using hydraulic spray nozzle the atomizationis produced by liquid pressure.

The catalyst support produced by the modified Spray Cooling method isprepared from an alcoholic solution comprising an inorganic compound, analcohol ROH, and an additive to increase the solubility of the inorganiccompound in the alcohol ROH:

In some embodiments, the inorganic compound can be a magnesium compound(such as a magnesium halide or/and magnesium alkoxide) which can bemixed with alcohol to form a solution. The alcohol has the formula ROH,wherein R is a C1-C18 hydrocarbon group, which enables the use of adifferent alcohol and therefore different molar ratios. For example, thealcohol can be methanol, ethanol, propanol, iso-propanol, butanol,isobutanol, 2-ethylhexanol, chloroethanol, 2,2,2-trichloroethanol. Theresulting mixture can be stirred at a temperature from 30° C. to 100°C., more specifically from 50° C. to 70° C. to form the alcoholicsolution.

The inorganic compound (e.g., magnesium compounds, such as magnesiumhalide or/and magnesium alkoxide) is mixed with alcohol and one or moreadditives, in which the additives can be fluorine based compounds suchas hydrofluoroalkenes (HFAs) or other compounds such aspolyaryletherketone (PAEK) derivatives, poly(oxy-1,2-ethanediyl)derivatives, aliphatic polyether, polylactic acid, and polysorbates.Examples of fluorine based compounds include: 2H, 3H perfluoropentane;1,1,1,2-tetrafluorethane; 1,1,1,2,3,3,3-heptafluoropentane;1,1,1,2,2,3,4-heptafluoropentane; 1,1,1,2,2,3,4-heptafluorobutane;1,1,3,3,4,4-hexafluorobutane; 1,1,1,2,3,4-hexafluorobutane;1,1,1,2,2,3,3,4,4-nonafluorohexane; 1,1,1,2,2,3,3,4,5-nonafluorohexane;1,1,1,2,2,3,3,4-octafluoropentane; 1,1,1,2,2,3,5-heptafluoropentane;1,1,1,2,2,3,4,5-octafluoropentane; and1,1,1,2,2,4,4,5,5-nonafluoropentane,1,1,1,2,3,4,4,5,5,5-decafluoropentane. Other examples of additivesinclude: sorbitan trifoliate, sorbitan monooleate, sorbitan monolaurate,polyoxyethylene sorbitan monolaurate, polyethylene sorbitan monooleate,natural lecithin, oleyl polyoxyethylene ether, stearyl polyoxyethyleneether, lauryl polyoxyethylene ether, block copolymers of oxyethylene andoxypropylene, oleic acid, synthetic lecithin, diethylene glycoldioleate, tetrahydrofurfuryl, oleate, ethyloleate, isopropyl myristate,glyceryl monooleate, glyceryl monostearate, glyceryl monoricinoleate,cetyl alcohol, polyethylene glycol, polyoxypropylene glycol, cetylpyridinium chloride, olive oil, glyceryl monolaurate, polyoxyethylenenonyl phenolether, polyoxyetheylene monolaurate, polyoxyethylenedilaurate, polyoxyethylene stearyl ether,polyetylenoglycol-b-polypropylene, oleic acid, polyetheretherketone,polyetherketone, polyetherketoneketone,polyetherketoneetherketoneketone, polyetheretherketoneketone. The amountof additive in the catalyst support can be between 0.01 to 20 wt %. Thealcohol ROH, wherein R is a C1-C18 hydrocarbon group.

The resulting alcoholic solutions described above can be aerosolized byspraying them through a nozzle, which is placed inside the reactor, asrepresented in FIG. 1. The aerosolized solutions can form a precipitatewhen contacted with an inert liquid at low temperature, between −30° C.to 0° C. As a result, generally spherical particles are obtained, asshown in FIG. 5.

The non-solvent or inert liquid can be a aliphatic and aromatichydrocarbon. The aliphatic hydrocarbon is selected from the groupconsisting of isoparaffin, hexane, heptane, octane, nonane, decane,cyclohexane or mixture of two or more hydrocarbon. The aromatichydrocarbon is selected from benzene, toluene, xylene or the mixture oftwo or more hydrocarbon.

The resulting catalytic support can be subjected to a heat treatment inorder to remove the excess of alcohol or additive compound or compounds.The amount of alcohol removed should correspond to a composition, inwhich the inorganic support obtained shows a molar ratio of at least 0.5mol of alcohol per mol of MgCl₂.

The catalyst for olefin polymerization is prepared by the reactionbetween the catalyst support as described above with one or moretitanium halides. Examples of the titanium halide include, but are notlimited to, titanium tetrachloride, titanium tetrabromide, tetrabutoxytitanium, tetraethoxy titanium, tributoxy titanium chloride, dibutoxytitanium dichloride, and triethoxy titanium. Titanium halide compoundsinclude those having chlorine (as titanium tetrachloride). The titaniumhalide can be used alone or in the presence of inert solvent. In someembodiments, the titanium halide component is added with an internaldonor compound such as a phthalate, succinate, diether, benzoate orchemically similar compound.

Embodiments of catalyst supports described in the present applicationwere obtained from alcoholic solutions of, comprising: (a) an inorganiccompound, being a magnesium compound and (b) an inorganic compound andone or more additives through a modified spray cooling technique to formgenerally spherical particles having differentiated physical propertiescompared known catalyst supports.

Some physical properties are exemplified in FIG. 2. DSC thermograms ofinventive supports SSB01 to SSB08 have endothermic peaks at threedifferent transition temperatures. The thermal transition “A” occursbetween 112° C. and 154° C.; thermal transition “B” occurs between 181°C. and 215° C.; and thermal transition “C” occurs between 235° C. and248° C.

In order to evaluate the effect of the aerosolization method, differenttypes of nozzles were used resulting in two different catalyst supportSSB04 (example 4) and SSB05 (example 5). The sample SSB04 was obtainedby the passage of the resulting alcoholic solution through a gasatomizing nozzle. The catalyst support SSB05 was produced by thehydraulic spray nozzle. The DSC thermograms show distinguishable thermalevents between SSB04 and SSB05, however in both cases, the mainendothermic peaks occurred at temperatures above 112° C.

In another embodiment, magnesium halide was mixed with an additive mono-(9Z)-9-octadecenoate, poly(oxy-1,2-ethanediyl) derivative (MOP) in thepresence of an alcohol to obtain sample SSB06 (having 1.4 wt % of MOPExample 06), and sample SSB07 having 4.8 wt % of MOP (Example 07). Asshown in FIG. 2, the addition of MOP in the initial alcoholic solutionalters the endothermic peaks of the final particles.

In yet another embodiment, an alcoholic solution was prepared withMgCl₂, 1.3 wt % of MOP, and 28.4 wt % of fluorine based compound1,1,1,2,3,4,4,5,5,5-decafluoropentane to produce sample SSB08 (Example8). As shown in FIG. 2, the addition of1,1,1,2,3,4,4,5,5,5-decafluoropentane further altered the endothermicpeaks of the final particles in a solution having MOP.

The inventive examples described herein were also analyzed by X-raydiffraction analysis. As shown in FIG. 3, the diffraction patterns ofthe catalyst supports (SSB01-SSB08) are different for differentexperiment conditions and also when compared to anhydrous MgCl₂, whichexhibits a cubic close packing structure that gives strong 2θ peaks at15°, 35°, and 50.4°.

Examples 01 to 03 describe catalyst supports SSB01 to SSB03,respectively, and show broad diffraction features observed at around5.6-6.1°. These results suggest the presence of an amorphous region inthe obtained inorganic particle. Furthermore, comparing the resultsmentioned in the cited patents, the obtained inorganic particles showedadditional XRD peaks with high intensity 2θ at 8.8° and 9.4° for SSB01and 8.3° for SSB02. The support SSB03, as described in example 3, wassubjected to a thermal treatment for partial elimination of alcohol andshowed a different diffraction pattern without a high intensity peakbelow 10°. High intensity reflection below 10° characterizes alcoholinteraction along the z-axis of layered structure of rhombohedral MgCl₂.

In order to evaluate the effect of the produced inorganic particle bydifferent types of nozzles, samples SSB04 and SSB05 were prepared asdescribed in the examples 4 and 5, respectively. The diffractionspectrum of these supports did not show high intensity diffraction peaksat 2θ above 10°, more specifically in between 10° and 50°. Inparticular, the sample SSB04 showed a single peak of greater intensityat 2θ=8.9° and a discrete peak at 2θ=9.4°. In contrast, sample SSB05showed a single low angle peak)(<10°, which was 2θ=8.3°. In the finalthree samples, it is important to mention that the introduction ofadditives aiming to improve the incorporation of MgCl₂ using alcohol asa solvating agent, systematically showed at least one low angle highintensity peak)(<10°. Sample SSB06, using 1.4 wt % of MOP, showed 2θdiffraction peaks at 8.9° and 9.3°. Otherwise, samples SSB07 and SSB08showed a single crystalline 2θ peak at 8.9° and 8.4°, respectively.Therefore, samples prepared as described in example 6 to 8 showed veryunique diffraction patterns. Although the additives improve theincorporation of MgCl₂ in alcohol, which act mainly as a solvationagent, they did not disturb crystalline adduct formation at low anglediffraction peaks. Furthermore, the results obtained in samples SSB05,SSB07, and SSB08 showed a single crystalline peak at 2θ below 10°.

Support Preparation

In some embodiments of the process to prepare a catalyst support, thecatalyst support can be prepared according to steps, comprising:

Step 1: Preparation of Alcoholic Solution

To prepare a solution of inorganic compound (e.g., magnesium compound)(4 wt % to 50 wt %) by dissolving in alcohol ROH with one or moreadditives (5 wt % to 50 wt %), which acts as solvation agent, all thecomponents are added to a glass reactor (FIG. 1) and the solution isprepared at temperatures below 100° C. (e.g., between 30° C. to 80° C.)under inert atmosphere (nitrogen or argon) in a stirring system usingmechanical or magnetic stirrer (e.g., between 100 RPM and 600 RPM).

Step 2: Preparation of the Support

The solution is stirred under a nitrogen atmosphere, slightlypressurized (1-5 bar) at a temperature below 100° C. (e.g., between 30°C. to 80° C.). The glass reactor is then connected to a transfer line orjacketed tubing, where the temperature is equal to or slightly higherthan the temperature of the alcoholic solution. The transfer line isthen connected to a nozzle (e.g., an atomizer) kept inside a secondreactor (e.g., reactor B of FIG. 1), which contains a non-solvent liquidat low temperature (−30° C. to 10° C.) under inert atmosphere (nitrogenor argon) slightly pressurized, which pressure is lower than a firstreactor (e.g., reactor A of FIG. 1), and stirred using a mechanicalstirrer (e.g., 100 RPM to 600 RPM). The alcoholic solution istransferred to the atomizer due to the higher pressure in first reactor(e.g., reactor A of FIG. 1)) and sprayed in a downward verticaldirection into small droplets (See, e.g., the atomizer/nozzle in reactorB of FIG. 1), which precipitate as generally spherical particles when incontact with the non-solvent liquid at low temperature (e.g., −30° C. to10° C.).

The resulting suspension of generally spherical particles and thenon-solvent liquid is stirred (e.g., 100 RPM to 600 RPM) at lowtemperature (e.g., −30° C. to 10° C.) for several hours (e.g., 0.1 h to6 h) before slowly warming the suspension to room temperature. The rateof crystallization of catalyst support depends upon residence time inthe liquid medium (e.g., in Reactor B of FIG. 1) the stirring conditions(e.g., rate of rotation), and temperature, which affects the morphologyand mechanical strength of the final solid particle. As a result, theseconditions can produce catalyst supports with different crystallinestructures.

The agitation/stirring is stopped to allow the spherical particles tosettle to the bottom of the reactor. The excess non-solvent liquid isseparated via cannula under inert atmosphere (e.g., nitrogen or argon)followed by the addition of excess hexane or heptane to transfer theresulting suspension to a Schlenk filter flask. Then, the non-solventsare flushed through the bottom of the flask under inert atmosphere(e.g., nitrogen or argon) retaining the generally spherical particles onthe filter.

The procedure is followed by an addition of hexane or heptane, which isstirred for 30 minutes under inert atmosphere and the liquids areflushed through the bottom of the Schlenk flask. This process isrepeated several times (e.g., 1 to 10 times) until the residualnon-solvent is removed. The resulting spherical particles are then driedunder nitrogen or argon flow for several hours (e.g., 1 h to 12 hs) toobtain the catalyst support.

Step 3: Thermal Treatment (Optional)

The spherical particles are added to or kept in a Schlenk filter flaskunder inert atmosphere (nitrogen or argon). The flask is placed insidean oven at initial temperature below 80° C. and under nitrogen or argonflow fluidizing the spherical support on the filter of the Schlenkflask. The thermal treatment can be carried out under isothermalconditions for several hours (e.g., 0.1 h to 12 hs) or temperature rampscan be performed up to 250° C. with ramp rates from 0.1° C./min to 100°C./min. Then, the spherical particles are cooled down to roomtemperature at cooling rates from 0.1° C./min to 100° C./min to obtainthe catalyst support.

EXAMPLES Example 1

A solution of MgCl₂ anhydride in ethanol at 4.0 wt % was prepared atroom temperature. This solution was transferred through ⅛″OD jacketedtubing with controlled temperature connected to an atomizer (gasatomizer nozzle) placed inside a 5 L rounded-bottom flask to spraydroplets of the alcoholic solution to dried isoparaffin at lowtemperature, approximately −20° C. The pressure applied in reactor A (1)and system (4) to transfer initial alcoholic solution to the atomizerwas 0.7 bar, while the N₂ pressure (5) was 1.0 bar. The resultingsuspension of the particles precipitated in isoparaffin was stirredovernight at 350 RPM. After stirring, the mixture was left for 3 hoursand then the supernatant was removed and 1 L of dried hexane was addedto form a suspension with the resulting particles. The resulting mixturewas transferred through cannula to a Schlenk flask followed by thefiltration and recovering of the particles, which was washed severaltimes with anhydride hexane and dried under nitrogen flow. All steps ofthis experiment were carried out under N₂ atmosphere to obtain supportsample SSB01.

Example 2

A solution of MgCl₂ anhydride in ethanol at 12.2 wt % was prepared at60° C. This solution was transferred through ⅛″OD jacketed tubing withcontrolled temperature directly to a 5 L rounded-bottom flask withoutthe use of the atomizer. The alcoholic solution was transferred to driedisoparaffin at low temperature, at approximately −20° C. The resultingsuspension of the particles precipitated in isoparaffin was stirredovernight at 350 RPM. After stirring, the mixture was left for 3 hoursand then the supernatant was removed and 1 L of dried hexane was addedto form a suspension with the resulting particles. The resulting mixturewas transferred through cannula to a Schlenk flask followed by thefiltration and recovering of the particles, which was washed severaltimes with anhydride hexane and dried under nitrogen flow. All steps ofthis experiment were carried out under N₂ atmosphere to obtain supportsample SSB02.

Example 3

The support catalyst was prepared as described in Example 2, followed byan additional step to remove the excess of ethanol from the obtainedparticles through a thermal treatment, as follows: the support wastransferred to a Schlenk filter and kept under countercurrent nitrogenflow inside an oven for 1 hour at each temperature 40° C., 50° C. and,60° C. to obtain support SSB03.

Example 4

A solution of MgCl₂ anhydride in ethanol at 12.2 wt % was prepared at60° C. This solution was transferred through ⅛″OD jacketed tubing withcontrolled temperature connected to an atomizer (gas atomizer nozzle)placed inside a 5 L rounded -bottom flask to spray droplets of thealcoholic solution to dried isoparaffin at low temperature,approximately −20° C. The pressure applied in reactor A (1) and system(4) to transfer initial alcoholic solution to the atomizer was 0.7 bar,while the N₂ pressure (5) was 1.0 bar. The resulting suspension of theparticles precipitated in isoparaffin was stirred overnight at 350 RPM.After stirring, the mixture was left for 3 hours and then thesupernatant was removed and 1 L of dried hexane was added to form asuspension with the resulting particles. Then, the resulting mixture wastransferred through cannula to a Schlenk flask followed by thefiltration and recovering of the particles, which was washed severaltimes with anhydride hexane and dried under nitrogen flow. All steps ofthis experiment were carried out under N₂ atmosphere to obtain supportsample SSB04.

Example 5

A solution of MgCl₂ anhydride in ethanol at 12.5 wt % was prepared at60° C. This solution was transferred through ⅛″OD jacketed tubing withcontrolled temperature connected to an atomizer (hydraulic spray nozzle)and placed inside a 5 L rounded -bottom flask to spray droplets of thealcoholic solution to dried isoparaffin at low temperature,approximately −20° C. The pressured applied in reactor A (1) and system(4) to transfer initial alcoholic solution to the atomizer was 1.0 bar.The resulting suspension of the particles precipitated in isoparaffinwas stirred overnight at 350 RPM. After stopping the stirring, themixture was left for 3 hours and then the supernatant was removed and 1L of dried hexane was added to form a suspension with the resultingparticles. Then, the resulting mixture was transferred through cannulato a Schlenk flask followed by the filtration and recovering of theparticles, which was washed several times with anhydride hexane anddried under nitrogen flow. All steps of this experiment were carried outunder N₂ atmosphere to obtain support sample SSB05.

Example 6

A solution of MgCl₂ anhydride in ethanol at 15.6 wt % was prepared at60° C. In this solution was added 1.4 wt % of MOP and then transferredthrough ⅛″OD jacketed tubing with controlled temperature connected to anatomizer (hydraulic spray nozzle) placed inside a 5 L rounded-bottomflask to spray droplets of the alcoholic solution to dried isoparaffinat low temperature, approximately −20° C. The pressure applied inreactor A (1) and system (4) to transfer initial alcoholic solution tothe atomizer was 1.0 bar. The resulting suspension of the particlesprecipitated in isoparaffin was stirred overnight at 350 RPM. Afterstopping the stirring, the mixture was left for 3 hours and then thesupernatant was removed and 1 L of dried hexane was added to form asuspension with the resulting particles. Then, the resulting mixture wastransferred through cannula to a Schlenk flask followed by thefiltration and recovering of the particles, which was washed severaltimes with anhydride hexane and dried under nitrogen flow. All steps ofthis experiment were carried out under N₂ atmosphere to obtain supportsample SSB06.

Example 7

A solution of MgCl₂ anhydride in ethanol at 18.0 wt % was prepared at60° C. In this solution was added 4.8 wt % of MOP and then transferredthrough ⅛″OD jacketed tubing with controlled temperature connected to anatomizer (hydraulic spray nozzle) placed inside a 5 L rounded-bottomflask to spray droplets of the alcoholic solution to dried isoparaffinat low temperature, approximately −20° C. The pressured applied inreactor A (1) and system (4) to transfer initial alcoholic solution tothe atomizer was 1.0 bar. The resulting suspension of the particlesprecipitated in isoparaffin was stirred overnight at 350 rpm. Afterstirring, the mixture was left for 3 hours and then the supernatant wasremoved and 1 L of dried hexane was added to form a suspension with theresulting particles. The resulting mixture was transferred throughcannula to a Schlenk flask followed by the filtration and recovering ofthe particles, which was washed several times with anhydride hexane anddried under nitrogen flow. All steps of this experiment were carried outunder N₂ atmosphere to obtain support sample SSB07.

Example 8

A solution of MgCl₂ anhydride in ethanol at 15.6 wt % was prepared at70° C. In this solution was added 1.3 wt % of MOP and 28.4 wt % of1,1,1,2,3,4,4,5,5,5-decafluoropentane. The resulting solution wastransferred through ⅛″OD jacketed tubing with controlled temperatureconnected to an atomizer (hydraulic spray nozzle) placed inside a 5 Lrounded-bottom flask to spray droplets of the alcoholic solution todried isoparaffin at low temperature, approximately −20° C. The pressureapplied in reactor A (1) and system (4) to transfer initial alcoholicsolution to the atomizer was 1.0 bar. The resulting suspension of theparticles precipitated in isoparaffin was stirred overnight at 350 RPM.After stirring, the mixture was left for 3 hours and then thesupernatant was removed and 1 L of dried hexane was added to form asuspension with the resulting particles. The resulting mixture wastransferred through cannula to a Schlenk flask followed by thefiltration and recovering of the particles, which was washed severaltimes with anhydride hexane and dried under nitrogen flow. All steps ofthis experiment were carried out under N₂ atmosphere to obtain supportsample SSB08.

Catalyst Synthesis

Example 9

To a 300 mL Schlenk flask equipped with a sealed mechanical stirrerunder N₂ atmosphere, 100 ml of TiCl₄ was added and the temperature wascooled down to 0° C. Then, 5.7 g of support (obtained from example 1 to8) was added and the mixture was stirred at 350 RPM followed by thedropwise addition of 22 ml of diisobutyl phthalate in hexane 10 wt %.The temperature of the reactive mixture was increased to 100° C. andstirred for 1 hour. The unreacted TiCl₄ and its residues were removed byfiltration followed by an additional 100 ml of TiCl₄ to remove undesiredremain residues. Thus, the resulting suspension was stirred for 1 hourat 120° C. and filtered again. The solid catalyst was washed severaltimes with anhydride hexane at 60° C. and dried under N₂ to obtaincatalysts SCB01 to SCB08, except for SCB05, which support sample SSB05was contaminated during the experiment. All residual TiCl₄ was quenchedwith ethanol/hexane mixture.

Polymerization of Propylene

Example 10

Propylene polymerizations were performance in bulk using a 3.8 Lstainless -steel reactor equipped with a mechanical stirrer, amanometer, a temperature indicator, a system for feeding the catalyst,monomer supply line, and a jacket for thermostatic temperature control.First, in a flask under N₂ atmosphere, 10 mg of catalyst was dispersedin 70 ml of hexane and then hexane solutions of triethyl aluminium 10 wt% and cyclohexylmethyl-dimethoxysilane 5 wt % were added. The pre-contact was left under stirring for 10 minutes. For propylenepolymerization, the reactor was purged with nitrogen flow at 70° C. for1 hour; then the catalyst dispersion was introduced into the reactorunder N₂ flow at 30° C. Hereafter, H₂ (1 bar) and 2.3 kg of liquidpropylene were fed under stirring. The temperature was raised to 70° C.and the polymerization was carried under this condition for 2 hours. Theunreacted propylene was flashed off and the resulting polymers SCB01-PPto SCB08-PP were recovered and dried at 70° C. under vacuum.

The application of the catalyst system of the present study is notlimited by propylene polymerization. It can be applied in polymerizationof other olefins.

Characterization

The obtained supports were characterized by atomic absorptionspectrometry analysis (AA) by Spectra A 50B Varian, potentiometrictitration was carried out in a 808 Titrando Metrohm andUltraviolet-visible spectrophotometry (UV-vis) in a Cary 100 Conc.Varian to quantify Mg (%), Cl (%); For thermal properties an evaluationsample was prepared in aluminum pans under nitrogen atmosphere to avoidexposure to moisture and analyzed by a differential scanning calorimeter(DSC) TA instrument, at a scanning rate of 10° C./min in the range 25°C. to 300° C. The samples were characterized by a Rigaku D/Max 2100Powder X-ray Diffractometer Cu Kα radiation (α=1.5405 Å) with adiffracted beam graphite monochromator. Scanning electron microscope(SEM) images were performed using TM1000-Hitach (Low Vacuum). Supportand catalyst average particle size and particle size distribution werecarried out by a laser light diffraction method using Apparatus MasterSizer Hydro 2000S from Malvern.

The resulting polypropylene xylenes solubles (XS) were measuredaccording to standard ASTM D 5492-06. Pentad analyses were carried outby ¹³C NMR spectrum in an Agilent 500 MHz at 120° C. in TCE-d/ODCB-d(1:1 v/v) equipped with a 5 mm probe. Gel permeation chromatography(GPC) was carried out on Alliance GPC 2000 from Waters using TCB as asolvent at 140° C. after calibration with standard polystyrene samples.Polymer powder measurements were carried out according to ASTM D1921-06.

TABLE 1 Elementary analysis of catalyst support Support (Mg) (%) Cl (%)SSB01 7.4 28.7 SSB02 8.6 35.7 SSB03 10.3 41.8 SSB04 8.0 29.7 SSB05 11.737.1 SSB06 8.8 56.0 SSB07 7.8 46.7 SSB08 7.3 22.1

TABLE 2 Elementary analysis of catalyst Catalyst^(a) (Mg) (%) Cl (%) Ti(%) SCB01 16.2 58.6 5.8 SCB02 13.8 58.9 6.4 SCB03 14.6 58.4 5.3 SCB0413.3 55.1 5.6 SCB05^(b) NA NA NA SCB06 13.3 56.0 6.9 SCB07 6.3 45.7 11.4SCB08 7.6 42.4 10.4 ^(a)Catalysts SCB01 to SCB08 were prepared fromtheir correspondent supports number SSB01 to SSB08. ^(b)The supportSSB05 was not used to prepare catalyst.

TABLE 3 Average particle diameter and Span Catalyst^(a) D50 (μm) SpanSCB01 24 2.8 SCB02 90 2.0 SCB03 122  1.9 SCB04 45 2.8 SCB05 NA NA SCB0672 1.8 SCB07 50 2.4 SCB08 54 2.3 ^(a)Catalysts SCB01 to SCB08 wereprepared from their correspondent supports number SSB01 to SSB08, exceptfrom support SSB05 which was not used to prepare catalyst.

TABLE 4 Catalyst performance and their correspondent polymers propertiesof SCB01-PP to SCB08-PP. Activity XS^(a) mmmm^(c) % powder^(e) Polymers(kg/g) (%) MFI MWD^(b) (mol %) <0.1 mm SCB01-PP  6 8.4 14.3 4.2 90.6 NASCB02-PP 30 5.7 11.7 3.7 92.5 0.4 SCB03-PP 24 4.8 17.9 4.1 88.8 1.4SCB04-PP 32 3.6 11.7 3.7 93.1 1.1 SCB05-PP^(d) NA NA NA NA NA NASCB06-PP 40 4.1 10.6 6.1 94.0 0.1 SCB07-PP 12 4.5 24.8 7.1 93.0 0.6SCB08-PP 10 4.3 23.8 7.1 93.1 1.5 ^(a)Wet method; ^(b)determined withGPC; ^(c)determined with ¹³C NMR; ^(d)SCB05 was not prepared;^(e)samples with activity below 10 kg of PP/g of catalyst were notmeasured.

What is claimed is:
 1. A catalyst support component comprising an inorganic compound, an alcohol ROH, and an additive, wherein the catalyst support component has a first thermal transition peak between 112° C. and 154° C. and a second thermal transition peak between 181° C. and 215° C. as shown by DSC.
 2. The catalyst support component of claim 1, having a third thermal transition peak between 235° C. and 248° C., as shown by DSC.
 3. The catalyst support component of claim 1, wherein the alcohol ROH consists of a R chosen from a C1-C18 hydrocarbon group.
 4. The catalyst support component of claim 1, wherein the additive is a fluorine-based additive.
 5. The catalyst support component of claim 1, wherein the additive is selected from one or more of hydrofluoroalkenes (HFAs), polyaryletherketone (PAEK) derivatives, poly(oxy-1,2-ethanediyl) derivatives, aliphatic polyethers, polylactic acid, or polysorbates.
 6. The catalyst support component of claim 4, wherein the additive is fluorine-based and selected from the group consisting of perfluoropentane;1,1,1,2-tetrafluorethane; 1,1,1,2,3,3,3-heptafluoropentane; 1,1,1,2,2,3,4-heptafluoropentane; 1,1,1,2,2,3,4-heptafluorobutane; 1,1,3,3,4,4-hexafluorobutane; 1,1,1,2,3,4-hexafluorobutane; 1,1,1,2,2,3,3,4,4-nonafluorohexane; 1,1,1,2,2,3,3,4,5-nonafluorohexane; 1,1,1,2,2,3,3,4-octafluoropentane; 1,1,1,2,2,3,5-heptafluoropentane; 1,1,1,2,2,3,4,5-octafluoropentane; 1,1,1,2,2,4,4,5,5-nonafluoropentane, and 1,1,1,2,3,4,4,5,5,5-decafluoropentane.
 7. The catalyst support component of claim 1, having at least one peak as shown by X-Ray diffraction, wherein only one peak is in the range from 0° to 10°.
 8. A process for the polymerization of olefins comprising contacting a monomer with an activated catalyst produced with the catalyst support component of claim
 1. 9. A catalyst support component comprising an inorganic compound, an alcohol ROH, and a fluorine-based additive selected from the group consisting of perfluoropentane; 1,1,1,2-tetrafluorethane; 1,1,1,2,3,3,3-heptafluoropentane; 1,1,1,2,2,3,4-heptafluoropentane; 1,1,1,2,2,3,4-heptafluorobutane; 1,1,3,3,4,4-hexafluorobutane; 1,1,1,2,3,4-hexafluorobutane; 1,1,1,2,2,3,3,4,4-nonafluorohexane; 1,1,1,2,2,3,3,4,5-nonafluorohexane; 1,1,1,2,2,3,3,4-octafluoropentane; 1,1,1,2,2,3,5-heptafluoropentane; 1,1,1,2,2,3,4,5-octafluoropentane; 1,1,1,2,2,4,4,5,5-nonafluoropentane, and 1,1,1,2,3,4,4,5,5,5-decafluoropentane.
 10. The catalyst support component of claim 9, having a first thermal transition peak between 112° C. and 154° C., as shown by DSC.
 11. The catalyst support component of claim 10, having a second thermal transition peak between 181° C. and 215° C., as shown by DSC.
 12. The catalyst support component of claim 11, having a third thermal transition peak between 235° C. and 248° C., as shown by DSC.
 13. The catalyst support component of claim 9, wherein the alcohol ROH consists of a R chosen from a C1-C18 hydrocarbon group.
 14. The catalyst support component of claim 9, having at least one peak as shown by X-Ray diffraction, wherein only one peak is in the range from 0° to 10°.
 15. A process for the polymerization of olefins comprising contacting a monomer with an activated catalyst produced with the catalyst support component of claim
 9. 